Two component mass polymerizable compositions containing polycycloolefin monomers and organoruthenium carbide precatalyst

ABSTRACT

Embodiments in accordance with the present invention encompass a two component composition containing in one component a latent organo-ruthenium carbide catalyst, and in another component a photoactive acid generator or a thermally active acid generator, and either of the components containing a mixture of photoactive compound along with one or more monomers which undergo ring open metathesis polymerization (ROMP) when said components are mixed together and exposed to a suitable radiation (or heat) to form a three-dimensional (3D) object. The three-dimensional objects so formed exhibits improved mechanical properties, particularly, high heat distortion temperature, impact strength, elongation to break, among others. Accordingly, compositions of this invention are useful as 3D inkjet materials for forming high impact strength objects of various sizes with microscale features lower than 100 microns, among various other uses.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.17/024,760, filed Sep. 18, 2020, now allowed, which claims the benefitof U.S. Provisional Application No. 62/901,853, filed Sep. 18, 2019;both of which are incorporated herein by reference in their entirety.

BACKGROUND OF THE INVENTION Field of the Invention

Embodiments in accordance with the present invention relate generally toa two component composition containing in two separate parts a masspolymerizable polycycloolefin monomer(s), an organoruthenium carbideprecatalyst and an activator which when mixed together and subjected tophotolytic or thermolytic conditions forms three dimensional (3D)objects, which are useful in 3D printing materials, among other uses.The two component compositions so formed are stable at ambientconditions and when mixed and photolyzed (or thermolyzed) form solidobjects which exhibit high mechanical properties, specifically, highimpact strength and high elongation to break. Thus compositions of thisinvention find utility in a variety of applications including as 3D inkcompositions, among others. More specifically, this invention relates toroom temperature stable two component compositions encompassingnorbornene (NB) and dicyclopentadiene (DCPD) based olefinic monomers andan organoruthenium carbide catalyst system which is activated underphotolytic (or thermolytic) conditions thereby undergoing masspolymerization to form solid objects, including films, vias, patternedlines, including photo-patterned images, among others.

Description of the Art

Recently there has been an increased interest in developing 3D inkcompositions which can produce 3D objects having finer structures atmicron levels. A few of the recently introduced 3D ink systems arecapable of continuous production of 3D objects which are useful in avariety of diversified applications including for example tissueengineering to electronic components. See for example, J. M. DeSimone etal., Science, Vol. 347, pp 1349-1352 (2015), where it is disclosed acontinuous liquid interface production (CLIP), which is controlled by a“dead zone” to avoid any oxygen sensitivity of the 3D ink materialsemployed therein, which allows fabrication of a series of objects atmuch faster speed and with high resolution such that the objects soformed can feature patterns in the 50 to 100 micron range.

WO2017/068590 A1 discloses a series of 3D inkjet printing materialsusing dicyclopentadiene compounds polymerizable by ring-openingmetathesis polymerization methods.

U.S. Pat. No. 9,909,022 B2 discloses various ink compositions which whenprinted and cured forms organic thin films on a substrate. Such inkcompositions are contemplated to be used in organic light emitting diode(OLED) displays. The compositions disclosed therein are generallycurable polyethylene glycol acrylates and polyol acrylates, which areknown to be unstable at temperatures higher than 200° C.

Piers, et al., Organometallics 2012, 31, 5634-5637, have shown thatcertain of the ruthenium carbide catalysts are active for ring openmetathesis polymerization of certain cycloalkenes. However, suchreactions are carried out in a solvent, and are thus not suitable as 3Dink materials for mass polymerization conditions.

Accordingly, there is still a need for developing 3D printing materialsthat can be cured at a faster speed and exhibit desirable thermal andmechanical properties for fabricating industrially useful 3D objects,films and patterned features at a lower cost, especially stable attemperatures higher than 200° C.

Thus, it is an object of this invention to provide 3D printingcompositions that overcome the gaps faced by the art. More specifically,it is an object of this invention to provide a two component compositionthat will mass polymerize rapidly when mixed together and photolyzed (orsubject to thermolytic conditions) under inert atmospheres to form 3Dobjects under the conditions of 3D printing system. It is further anobject of this invention to provide stable two component masspolymerizable composition with no change in viscosity at or below normalstorage conditions but which undergoes mass polymerization only whenmixed together under the 3D process conditions.

Other objects and further scope of the applicability of the presentinvention will become apparent from the detailed description thatfollows.

SUMMARY OF THE INVENTION

Surprisingly, it has now been found that by employing a two componentfiller composition, it is now possible to form three dimensional objectshaving improved thermal and mechanical properties, most notably, the twocomponent compositions of this invention can be tailored to desirablethermo-mechanical properties. For example, the compositions of thisinvention can be tailored to exhibit glass transition temperatures(T_(g)) higher than 150° C., high heat distortion temperature (HDT,higher than 50° C. at 1.82 MPa/264 psi), high elongation to break(greater than 100 percent), high impact strength (Izod impact strengthof about 50 J/m or higher) and high tensile strength (greater than 50MPa). It is also important to note that the compositions of thisinvention can be mass polymerized under photolytic conditions at afaster speed and thus can be employed in any of the 3D technologies,including layer by layer approach, inkjet formulations and in thestereolithographic applications involving continuous liquid interfaceproduction of 3D objects. The compositions of this invention areexpected to exhibit faster photopolymerizing capabilities thus enablingto form a wide variety of objects of different sizes, including sizesgreater than 10 inches and structural details lower than 50 μm. Further,compositions of this invention are also expected to exhibit lowshrinkage due to their rigid polycycloolefinic structure. In addition,as the components of this invention undergo fast mass polymerizationupon application they do not leave behind any fugitive small moleculeswhich needs further processing. Generally, no other small moleculeadditives need to be employed thus offering additional advantages. Mostimportantly, the two component compositions of this invention are stable(i. e., no change in viscosity) at ambient atmospheric conditionsincluding up to 35° C. for several days, and undergo mass polymerizationonly when mixed together under photolytic conditions.

In another aspect of this invention there is also provided a kitencompassing the two component composition of this invention for forminga three dimensional object.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments in accordance with the present invention are described belowwith reference to the following accompanying figures and/or images.Where drawings are provided, it will be drawings which are simplifiedportions of various embodiments of this invention and are provided forillustrative purposes only.

FIGS. 1A and 1B show optical micrographs of different resolutions oftypical patterned surface of a conventional digital video disk (DVD):FIG. 1A—20 μm and FIG. 1B—10 μm.

FIGS. 2A and 2B show optical micrographs of different resolutions ofpatterned surface obtained from a composition embodiment of thisinvention: FIG. 1A—20 μm and FIG. 1B—10 μm, which are identical replicaof the patterned surface of a DVD.

DETAILED DESCRIPTION

The terms as used herein have the following meanings:

As used herein, the articles “a,” “an,” and “the” include pluralreferents unless otherwise expressly and unequivocally limited to onereferent.

Since all numbers, values and/or expressions referring to quantities ofingredients, reaction conditions, etc., used herein and in the claimsappended hereto, are subject to the various uncertainties of measurementencountered in obtaining such values, unless otherwise indicated, allare to be understood as modified in all instances by the term “about.”

Where a numerical range is disclosed herein such range is continuous,inclusive of both the minimum and maximum values of the range as well asevery value between such minimum and maximum values. Still further,where a range refers to integers, every integer between the minimum andmaximum values of such range is included. In addition, where multipleranges are provided to describe a feature or characteristic, such rangescan be combined. That is to say that, unless otherwise indicated, allranges disclosed herein are to be understood to encompass any and allsub-ranges subsumed therein. For example, a stated range of from “1 to10” should be considered to include any and all sub-ranges between theminimum value of 1 and the maximum value of 10. Exemplary sub-ranges ofthe range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8,and 5.5 to 10, etc.

As used herein, the expression “alkyl” means a saturated, straight-chainor branched-chain hydrocarbon substituent having the specified number ofcarbon atoms. Particular alkyl groups are methyl, ethyl, n-propyl,isopropyl, tert-butyl, and so on. Derived expressions such as “alkoxy”,“thioalkyl”, “alkoxyalkyl”, “hydroxyalkyl”, “alkylcarbonyl”,“alkoxycarbonylalkyl”, “alkoxycarbonyl”, “diphenylalkyl”, “phenylalkyl”,“phenylcarboxyalkyl” and “phenoxyalkyl” are to be construed accordingly.

As used herein, the expression “cycloalkyl” includes all of the knowncyclic groups. Representative examples of “cycloalkyl” includes withoutany limitation cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, and the like. Derived expressions such as“cycloalkoxy”, “cycloalkylalkyl”, “cycloalkylaryl”, “cycloalkylcarbonyl”are to be construed accordingly.

As used herein, the expression “perhaloalkyl” represents the alkyl, asdefined above, wherein all of the hydrogen atoms in said alkyl group arereplaced with halogen atoms selected from fluorine, chlorine, bromine oriodine. Illustrative examples include trifluoromethyl, trichloromethyl,tribromomethyl, triiodomethyl, pentafluoroethyl, pentachloroethyl,pentabromoethyl, pentaiodoethyl, and straight-chained or branchedheptafluoropropyl, heptachloropropyl, heptabromopropyl, nonafluorobutyl,nonachlorobutyl, undecafluoropentyl, undecachloropentyl,tridecafluorohexyl, tridecachlorohexyl, and the like. Derivedexpression, “perhaloalkoxy”, is to be construed accordingly. It shouldfurther be noted that certain of the alkyl groups as described herein,such as for example, “alkyl” may partially be fluorinated, that is, onlyportions of the hydrogen atoms in said alkyl group are replaced withfluorine atoms and shall be construed accordingly.

As used herein the expression “acyl” shall have the same meaning as“alkanoyl”, which can also be represented structurally as “R—CO—,” whereR is an “alkyl” as defined herein having the specified number of carbonatoms. Additionally, “alkylcarbonyl” shall mean same as “acyl” asdefined herein. Specifically, “(C₁-C₄)acyl” shall mean formyl, acetyl orethanoyl, propanoyl, n-butanoyl, etc. Derived expressions such as“acyloxy” and “acyloxyalkyl” are to be construed accordingly.

As used herein, the expression “aryl” means substituted or unsubstitutedphenyl or naphthyl. Specific examples of substituted phenyl or naphthylinclude o-, p-, m-tolyl, 1,2-, 1,3-, 1,4-xylyl, 1-methylnaphthyl,2-methylnaphthyl, etc. “Substituted phenyl” or “substituted naphthyl”also include any of the possible substituents as further defined hereinor one known in the art.

As used herein, the expression “arylalkyl” means that the aryl asdefined herein is further attached to alkyl as defined herein.Representative examples include benzyl, phenylethyl, 2-phenylpropyl,1-naphthylmethyl, 2-naphthylmethyl and the like.

As used herein, the expression “alkenyl” means a non-cyclic, straight orbranched hydrocarbon chain having the specified number of carbon atomsand containing at least one carbon-carbon double bond, and includesethenyl and straight-chained or branched propenyl, butenyl, pentenyl andhexenyl groups. Derived expression, “arylalkenyl” and five membered orsix membered “heteroarylalkenyl” is to be construed accordingly.Illustrative examples of such derived expressions includefuran-2-ethenyl, phenylethenyl, 4-methoxyphenylethenyl, and the like.

As used herein, the expression “heteroaryl” includes all of the knownheteroatom containing aromatic radicals. Representative 5-memberedheteroaryl radicals include furanyl, thienyl or thiophenyl, pyrrolyl,isopyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isothiazolyl,and the like. Representative 6-membered heteroaryl radicals includepyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the likeradicals. Representative examples of bicyclic heteroaryl radicalsinclude, benzofuranyl, benzothiophenyl, indolyl, quinolinyl,isoquinolinyl, cinnolyl, benzimidazolyl, indazolyl, pyridofuranyl,pyridothienyl, and the like radicals.

“Halogen” or “halo” means chloro, fluoro, bromo, and iodo.

In a broad sense, the term “substituted” is contemplated to include allpermissible substituents of organic compounds. In a few of the specificembodiments as disclosed herein, the term “substituted” meanssubstituted with one or more substituents independently selected fromthe group consisting of (C₁-C₆)alkyl, (C₂-C₆)alkenyl,(C₁-C₆)perfluoroalkyl, phenyl, hydroxy, —CO₂H, an ester, an amide,(C₁-C₆)alkoxy, (C₁-C₆)thioalkyl and (C₁-C₆)perfluoroalkoxy. However, anyof the other suitable substituents known to one skilled in the art canalso be used in these embodiments.

It should be noted that any atom with unsatisfied valences in the text,schemes, examples and tables herein is assumed to have the appropriatenumber of hydrogen atom(s) to satisfy such valences.

By the term “latent organo-ruthenium carbide catalyst” is meantorgano-ruthenium carbide compounds that show little or no catalyticactivity at a particular (usually ambient atmospheric conditions)temperature and initiate such activity upon exposure to suitableradiation.

By the term “three dimensional object” or “3D object” means any of themacroscale or microscale objects that can be formed from thecompositions of this invention by any of the known techniques having awide variety of applications including electronic, optoelectronic, andother applications.

By the term “derived” is meant that the polymeric repeating units arepolymerized (formed) from, for example, polycyclic monomers, such asnorbornene-type monomers in accordance with formulae (I) or (IV) whereinthe resulting polymers are ring opened metathesis polymerized (ROMP),for example, the 2,3 double bond of norbornene-type monomers are ringopened and polymerized as shown below:

Accordingly, in accordance with the practice of this invention there isprovided a two component composition comprising component A andcomponent B, wherein component A contains a latent organo-rutheniumcarbide catalyst and component B contains a photoactive or athermoactive acid generator and either of the component A or thecomponent B further comprising:

a) one or more monomers of formula (I):

wherein:

m is an integer 0, 1 or 2;

is a single bond or a double bond;

R₁, R₂, R₃ and R₄ are the same or different and each independentlyselected from the group consisting of hydrogen, halogen, methyl, ethyl,linear or branched (C₃-C₁₆)alkyl, (C₂-C₁₆)alkenyl,perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl,(C₇-C₁₄)tricycloalkyl, methoxy, ethoxy, linear or branched(C₃-C₁₆)alkoxy, (C₂-C₆)acyl, (C₂-C₆)acyloxy, perfluoro(C₆-C₁₄)aryl,perfluoro(C₆-C₁₄)aryl(C₁-C₃)alkyl, (C₆-C₁₄)aryloxy,(C₆-C₁₄)aryl(C₁-C₆)alkoxy, tri(C₁-C₆)alkoxysilyl and a group of formula(A):—Z-Aryl  (A)

-   -   wherein:    -   Z is a bond or a group selected from the group consisting of:    -   (CR₅R₆)_(a), O(CR₅R₆)_(a), (CR₅R₆)_(a)O,        (CR₅R₆)_(a)—O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O—(SiR₅R₆)_(b),        (CR₅R₆)_(a)—(CO)O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O(CO)—(CR₅R₆)_(b),        (CR₅R₆)_(a)—(CO)—(CR₅R₆)_(b), where a and b are integers which        may be the same or different and each independently is 1 to 12;

R₅ and R₆ are the same or different and each independently selected fromthe group consisting of hydrogen, methyl ethyl, linear or branched(C₃-C₆)alkyl, methoxy, ethoxy, linear or branched (C₃-C₆)alkyloxy,(C₂-C₆)acyl, (C₂-C₆)acyloxy, phenyl and phenoxy;

Aryl is selected from the group consisting of phenyl, biphenyl andnaphthyl, where the aryl is optionally substituted with one or more ofgroups selected from the group consisting of methyl, ethyl, linear orbranched (C₃-C₆)alkyl, hydroxy, methoxy, ethoxy, linear or branched(C₃-C₆)alkyloxy, (C₂-C₆)acyl, (C₂-C₆)acyloxy, phenyl and phenoxy; or

one of R₁ or R₂ taken together with one of R₃ or R₄ and the carbon atomsto which they are attached to form a (C₅-C₇)carbocyclic ring optionallycontaining one or more double bonds; and

b) a photoactive compound; and

wherein said latent organo-ruthenium carbide catalyst is of formula (II)or formula (III):

wherein:

L is PR₃, where R is independently selected from the group consisting ofisopropyl, sec-butyl, tert-butyl, cyclohexyl, bicyclo(C₅-C₁₀)alkyl,phenyl, benzyl, isopropoxy, sec-butoxy, tert-butoxy, cyclohexyloxy,phenoxy and benzyloxy;

R₇ is selected from the group consisting of methyl, ethyl, isopropyl,sec-butyl, tert-butyl, substituted or unsubstituted cyclohexyl,substituted or unsubstituted phenyl, substituted or unsubstitutedbiphenyl and substituted or unsubstituted naphthyl;

R₈ and R₉ are the same or different and each independently selected fromthe group consisting of hydrogen, methyl, ethyl, linear or branched(C₁-C₆)alkyl, (C₆-C₁₀)aryl, methoxy, ethoxy, linear or branched(C₁-C₆)alkoxy, (C₆-C₁₀)aryloxy, —NHCO(C₁-C₆)alkyl,—NHCO-perfluoro(C₁-C₆)alkyl, —SO₂N((C₁-C₆)alkyl)₂ and —NO₂; or

R₈ and R₉ taken together with the carbon atom to which they are attachedto form a (C₃-C₇)cycloalkyl ring;

-   -   each R₁₀ is independently selected from the group consisting of        hydrogen, methyl, ethyl and linear or branched (C₁-C₆)alkyl;

Ar₁ and Ar₂ are the same or different and each independently selectedfrom the group consisting of substituted or unsubstituted phenyl,substituted or unsubstituted biphenyl and substituted or unsubstitutednaphthyl;

wherein said substituents are selected from the group consisting ofmethyl, ethyl, iso-propyl, tert-butyl and phenyl; and wherein saidcomponent A and component B are in a clear liquid form at roomtemperature.

As used herein the Aryl may further include the following:

substituted or unsubstituted biphenyl of formula:

substituted or unsubstituted naphthyl of formula:

substituted or unsubstituted terphenyl of formula:

substituted or unsubstituted anthracenyl of formula:

substituted or unsubstituted fluorenyl of formula:

where R_(x) in each occurrence is independently selected from methyl,ethyl, linear or branched (C₃-C₁₂)alkyl or (C₆-C₁₀)aryl.

The composition of this invention can contain additional types ofcycloalkenes in either of component A or component B. Accordingly, insome embodiments, either of the component A or the component B of thisinvention further comprises one or more monomers of formula (IV):

wherein

R₁₆ and R₁₇ are the same or different and each independently selectedfrom the group consisting of hydrogen, methyl ethyl, linear or branched(C₃-C₆)alkyl, methoxy, ethoxy, linear or branched (C₃-C₆)alkyloxy,acetoxy, (C₂-C₆)acyl, phenyl and phenoxy; or

R₁₆ taken together with R₁₇ and the carbon atoms to which they areattached to form a (C₅-C₇)carbocyclic ring optionally containing one ormore double bonds;

R₁₈ is hydrogen, halogen, methyl, ethyl, linear or branched(C₃-C₁₆)alkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₆)alkyl, hydroxy, methoxy,ethoxy, linear or branched (C₃-C₁₆)alkoxy, (C₆-C₁₀)aryloxy,(C₆-C₁₀)aryl(C₁-C₆)alkoxy, —O(CO)R₁₉ and —O(CO)OR₁₉, where R₁₉ ismethyl, ethyl, linear or branched (C₃-C₁₆)alkyl, (C₆-C₁₀)aryl and(C₆-C₁₀)aryl(C₁-C₆)alkyl.

Advantageously, it has further been found that the compositions of thisinvention can contain even further additional monomers. In someembodiments, the composition according to this invention may furthercontain one or more second monomer selected from the monomer of formula(VII).

wherein:

o is an integer from 0 to 2, inclusive;

D is SiR₂₂R₂₃R₂₄ or a group selected from:—(CH₂)_(c)—O—SiR₂₂R₂₃R₂₄  (E);—(CH₂)_(c)—SiR₂₂R₂₃R₂₄  (F); and—(SiR₂₂R₂₃)_(c)—O—SiR₂₂R₂₃R₂₄  (G); wherein

c is an integer from 1 to 10, inclusive, and where one or more of CH₂ isoptionally substituted with (C₁-C₁₀)alkyl, (C₁-C₁₀)perfluoroalkyl or(C₆-C₁₄)aryl;

R₁₉, R₂₀ and R₂₁ are the same or different and independently of eachother selected from hydrogen, halogen and hydrocarbyl, where hydrocarbylis selected from methyl, ethyl, linear or branched (C₃-C₁₂)alkyl,(C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl,(C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₁-C₁₂)alkoxy,(C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy,(C₆-C₁₀)aryloxy(C₁-C₃)alkyl or (C₆-C₁₀)aryloxy; and

R₂₁, R₂₂ and R₂₃ are each independently of one another methyl, ethyl,linear or branched (C₃-C₉)alkyl, substituted or unsubstituted(C₆-C₁₄)aryl, methoxy, ethoxy, linear or branched (C₃-C₉)alkoxy orsubstituted or unsubstituted (C₆-C₁₄)aryloxy.

In this aspect of the invention, it has now been found that monomers offormula (VII) provides further advantages. Namely, the monomers offormula (VII) depending upon the nature of the monomer may impart highthermo-mechanical properties, thus it can be tailored to meet the need.In addition, the monomers of formula (VII) may exhibit low viscosity andgood solubility for the latent catalyst and/or activator, among variousother advantages.

Again, any amount of one or more monomers of formula (I) with one ormore monomers of formula (IV) can be employed to form the compositionsof this invention, and if necessary, one or more monomers of formula(VII). Accordingly, the combined molar ratio of monomers of formula (I)to monomers of formula (IV) can be from 1:99 to 99:1. In someembodiments, the molar ratio of monomers of formula (I):monomers offormula (IV) is in the range from 5:95 to 95:5; in some otherembodiments it is from 10:90 to 90:10; it is from 20:80 to 80:20; it isfrom 30:70 to 70:30; it is from 60:40 to 40:60; and it is 50:50, and soon. Similarly, when more than one monomer of formula (I) and more thanone monomer of formula (IV) are employed, any ratios of such monomerscan be used that would bring about the intended result. Similarly, anyamount of one or more monomers of formula (VII) can also be employeddepending upon the intended benefit such monomers may afford.

All of the aforementioned monomers employed in the composition of thisinvention are themselves known in the literature or can be prepared byany of the known methods in the art to make such or similar types ofmonomers.

In addition, the monomers as described herein readily undergo masspolymerization, i.e., substantially in their neat form without use ofany solvents when polymerized under mass ring open metathesispolymerization (ROMP) conditions using certain transition metalcatalysts, such as for example, organo-ruthenium and organo-osmiumcompounds. See for example, R. H. Grubbs et al., Handbook of Metathesis,Ed.: Wiley-VCH, Weinheim, Germany, 2003, R. H. Grubbs et al., Acc. Chem.Res. 2001, 34, 18-29, R. H. Grubbs et al., Angew. Chem. Int. Ed., 2006,45, 3760-3765. Also, see U.S. Pat. No. 6,838,489, pertinent portions ofwhich are incorporated herein by reference. The term “masspolymerization” as used herein shall have the generally accepted meaningin the art. That is, a polymerization reaction that is generally carriedout substantially in the absence of a solvent. In some cases, however, asmall proportion of solvent is present in the reaction medium. Forexample, such small amounts of solvent may be used to dissolve thelatent catalyst and/or the activator, including photoactive (orthermoactive) acid generator or convey the same to the reaction medium.Also, some solvent may be used to reduce the viscosity of the monomer orto dissolve the monomer if it is in a solid form. In some cases theco-monomer, if employed, may itself serve as a solvent both to reducethe viscosity and/or to dissolve the co-monomer. The amount of solventthat can be used in the reaction medium may be in the range of 0 to 10weight percent based on the total weight of the monomers employed or maybe higher. In some embodiments the amount of solvent used is less thanone weight percent based on the total weight of the monomers (or thetotal composition, including component A and B) employed. In some otherembodiments the amount of solvent used is less than two weight percentbased on the total weight of the monomers (or the total composition,including component A and B) employed. Any of the suitable solvents thatdissolve the catalyst, activator and/or monomers can be employed in thisinvention. Examples of such solvents include alkanes, cycloalkane,toluene, THF, dichloromethane, dichloroethane, and the like.

Advantageously, it has now been found that one or more of the monomersthemselves can be used to dissolve the latent catalyst as well as theactivator and thus avoiding the need for the use of solvents. Inaddition, one monomer can itself serve as a solvent for the othermonomer and thus eliminating the need for an additional solvent. Forexample, if first monomer of formula (I) is a solid at room temperature,then the second monomer of formula (I), which is liquid at roomtemperature can be used as a solvent for the first monomer of formula(I) which is a solid or vice versa. Therefore, in such situations morethan one monomer can be employed in the composition of this invention.

Accordingly, it has now been surprisingly found that monomers of formula(I) serve as raw materials for fabricating a three dimensional (3D)objects using any of the known 3D technologies. In general, thecomposition of this invention exhibits low viscosity, which can be below100 centipoise at 25° C. and in some embodiments below 50 centipoise(cP) at room temperature (i.e., around 25° C.). In some embodiments, theviscosity of the composition of this invention is less than 40centipoise at 25° C. In some other embodiments the viscosity of thecomposition of this invention is in the range from about 10 to 40centipoise at 25° C. In yet some other embodiments the viscosity of thecomposition of this invention is lower than 30 cP, lower than 20 cP,lower than 15 cP, lower than 12 cP at 25° C. In some embodiments it maybe lower than 10 cP at 40° C. In some embodiments the viscosity of thecomposition of this invention is in the range from about 8 to 12 cP at40° C. Accordingly, in some embodiments the composition according tothis invention contains in either of the component A or the component Ba first and a second monomer of formula (I) distinct from each other andone of said first and second monomers having a viscosity below 50centipoise at 25° C., and wherein said first monomer is completelymiscible with said second monomer to form a clear solution.

When the composition of this invention contains two or more monomers,for example, they can be present in any desirable amounts that wouldbring about the intended benefit, including viscosity modification orimprovement in thermal and mechanical properties or both. Accordingly,the molar ratio of first monomer of formula (I) to second distinctmonomer of formula (I) can be from 1:99 to 99:1. In some embodiments,the molar ratio of first monomer of formula (I):second distinct monomerof formula (I) is in the range from 5:95 to 95:5; in some otherembodiments it is from 10:90 to 90:10; it is from 20:80 to 80:20; it isfrom 30:70 to 70:30; it is from 60:40 to 40:60; and it is 50:50, and soon. Similarly, when more than two different monomers of formula (I) areemployed, any ratios of such monomers can be used that would bring aboutthe intended result.

In general, the compositions in accordance with the present inventionencompass the above described one or more of the monomer of formula (I)and if needed additional monomers of formula (I) distinct from eachother, or one or more monomers of formula (IV) or one or more monomersof formula (VII), as it will be seen below, various compositionembodiments are selected to provide properties to such embodiments thatare appropriate and desirable for the use for which such embodiments aredirected, thus such embodiments are tailorable to a variety of specificapplications.

For example, as already discussed above, proper combination ofdistinctive monomers of formula (I) makes it possible to tailor acomposition having the desirable viscosity, thermal and mechanicalproperties. In addition, as described further herein it may be desirableto include other polymeric or monomeric materials as additives, such asfor example inorganic nanoparticles which are compatible to providedesirable optical properties depending upon the end use application.Accordingly, the compositions of this invention can also include otherpolymeric materials and/or nanoparticles which will bring about suchintended benefit. Examples of such polymers include without anylimitation, polystyrene, poly(α-methylstyrene), poly(vinyl-toluene),copolymers of α-methylstyrene and vinyl-toluene, and the like. Otherpolymers that may be suitable as additives in the compositions of thisinvention include elastomeric polymers, including a wide variety ofrubbers, both natural and synthetic rubber. Non-limiting examples ofsynthetic rubbers include polyisobutylene (PIB), polybutadiene,polyisoprene, random and block copolymers of butadiene and/or isoprenewith styrene, styrene-butadiene rubbers (SBR), chloroprene rubbers, andthe like. In some embodiments certain of these polymers and/ornanoparticles also function as viscosity modifiers depending upon thetype of monomers employed. Accordingly, in some embodiments of thisinvention polystyrene is used as viscosity modifier.

The compositions in accordance with the present invention may furthercontain optional additives as may be useful for the purpose of improvingproperties of both the composition and the resulting object madetherefrom. Such optional additives for example may include anti-oxidantsand synergists. Any of the anti-oxidants that would bring about theintended benefit can be used in the compositions of this invention.Non-limiting examples of such antioxidants include pentaerythritoltetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (IRGANOX™ 1010from BASF), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl esterbenzenepropanoic acid (IRGANOX™ 1076 from BASF) and thiodiethylenebis[3-(3,5-di-tert.-butyl-4-hydroxy-phenyl)propionate] (IRGANOX™ 1035from BASF).

In some embodiments the composition according to this inventionencompasses a monomer of formula (I) wherein m is 1 and each of R₁, R₂,R₃ and R₄ are hydrogen. In some other embodiments the compositionaccording to this invention encompasses a monomer of formula (I) whereinm is 0 and at least one of R₁, R₂, R₃ and R₄ is other than hydrogen andis a group as defined above and the remaining R₁, R₂, R₃ and R₄ arehydrogen.

In some embodiments the composition according to this inventionencompasses a monomer of formula (IV) where R₁₈ is hydrogen. In someembodiments the composition according to this invention encompasses amonomer of formula (IV) where R₁₈ is methyl, ethyl, n-propyl,iso-propyl, n-butyl, iso-butyl, tert-butyl, phenyl, benzyl, phenethyl,methoxy, ethoxy, phenoxy, benzyloxy, acetoxy and benzoyl.

In some embodiments the composition of this invention encompasses firstand second monomer of formula (I) distinct from each other, wherein saidfirst monomer is of formula (I) wherein m is 1 and each of R₁, R₂, R₃and R₄ are hydrogen; and wherein said second monomer is of formula (I)wherein m is 0, R₁ is decyl and each of R₂, R₃ and R₄ are hydrogen.

Accordingly, any of the monomers within the scope of monomer of formula(I) can be employed in the composition of the invention. Representativeexamples of monomer of formula (I) include the following without anylimitations:

Representative examples of monomer of formula (IV) include the followingwithout any limitations:

In some embodiments the composition of this invention encompasses one ormore monomer of formula (I), which is selected from the group consistingof:

tetracyclododecene (TD);

5-butylbicyclo[2.2.1]hept-2-ene (BuNB);

5-hexylbicyclo[2.2.1]hept-2-ene (HexylNB);

5-decylbicyclo[2.2.1]hept-2-ene (DecylNB);

5-phenethylbicyclo[2.2.1]hept-2-ene (PENB);

5-(2-([1,1′-biphenyl]-4-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene; and

5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene(NBEtO-2-PhPh).

In some embodiments the composition of this invention further includes amonomer of formula (IV), which is dicyclopentadiene (DCPD). It should benoted that mixtures in any combination of aforementioned monomers offormula (I) and monomers of formula (IV) can be employed in thecompositions of this invention so as to obtain the intended benefit forforming the desirable 3D objects and can be tailored in accordance withthe properties required for the formation of such 3D objects.

In a further embodiment of this invention, the composition contains anyof the latent organoruthenium carbide catalyst that would bring aboutthe mass polymerization as described herein under ROMP conditions.Generally, such suitable latent catalysts include at least one knownorgano-ruthenium carbide complex of formula (II). See for example, Pierset al., Organometallics, 2012, 31, 5634-5637, disclose a series oforgano-ruthenium carbide compounds, which are pre-catalysts for theolefin metathesis reactions, all of such catalysts may be suitable aslatent catalysts in the compositions of this invention.

In some embodiments the latent catalyst which is an organo-rutheniumcarbide is of formula (III):

wherein:

L is PR₃, where R is independently selected from the group consisting ofisopropyl, sec-butyl, tert-butyl, cyclohexyl and phenyl;

each R₈, R₉ and R₁₀ is independently selected from the group consistingof hydrogen, methyl, ethyl, n-propyl, iso-propyl and phenyl;

Ar₂ is selected from the group consisting of 2,4-dimethylphenyl,2,4-diethylphenyl, 2,4-diisopropylphenyl and 2,4,6-trimethylphenyl.

Generally, any of the latent organo-ruthenium carbide catalyst thatwould bring about ring open metathesis polymerization of the monomers offormula (I) and monomer of formula (IV) as well as monomer of formula(VII), if present, can be employed in the composition of this invention.More specifically, organo-ruthenium carbide compounds that show littleor no activity at ambient temperatures can be employed. That is, thelatent catalysts that are stable at or near room temperature are moresuitable in the composition of this invention. The latent catalysts maybe activated by a variety of conditions, including without anylimitation acid and chemical activation. The chemical activation mayinclude use of thermal acid generators or photo acid generators.

Several of the latent catalysts that are suitable to be employed in thecompositions of this invention are known in the literature or can bereadily made by any of the known procedures in the art. See for example,Grubbs, et al., Organometallics, 2011, 30 (24): 6713-6717; Sutar et al.,Angew. Chem. Int. Ed. 2016, 55, 764-767; Leitgeh, et al., Monatsh Chem(2014) 145:1513-1517; van Hensbergen, et al., J. Mater. Chem. C. 2015,3, 693-702; Grubbs, et al., J. Am. Chem. Soc., 2009, 131, 203802039;Zak, et al., Eur. J. Inorg. Chem., 2014, 1131-1136; Gawin, et al., ACSCatal. 2017, 7, 5443-5449. As noted above, further examples of suchcatalysts can also be found in Piers et al. Accordingly, a few of theexemplary latent catalysts, which are organo-ruthenium carbidecompounds, without any limitation maybe selected from the groupconsisting of:

As noted, the composition of this invention further contains aphotoactive compound, which is generally a photosensitizer compound thatcan accelerate the formation of the acid from the photoacid generatorwhen subjected to radiation at a particular wavelength. For thispurpose, any suitable sensitizer compound can be employed in thecompositions of the present invention.

Such suitable sensitizer compounds include, photosensitizers, such as,anthracenes, phenanthrenes, chrysenes, benzpyrenes, fluoranthenes,rubrenes, pyrenes, xanthones, indanthrenes, thioxanthen-9-ones,phenothiazine, and mixtures thereof. Surprisingly it has now been foundthat certain of the known photoactive compounds, such as for example, aclass of substituted xanthone derivatives can be used for this purpose.These photosensitizers are generally active at wavelengths from around200 to 400 nm, and some around 240 to 370 nm.

Accordingly, in some embodiments such xanthone derivatives are of theformula (V):

Wherein X is hydrogen or chlorine, R₃₀ and R₃₁ are the same or differentand independently of each other selected from hydrogen, chlorine,methyl, ethyl, linear or branched (C₃-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl,(C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl,(C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy,(C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy,(C₆-C₁₀)aryloxy(C₁-C₃)alkyl and (C₆-C₁₀)-aryloxy. In some otherembodiments R₃₀ is hydrogen and R₃₁ is selected from the groupconsisting of methoxy, ethoxy, n-propoxy, iso-propoxy, butoxy, and thelike.

Further, it has also been found that a variety of substituted triazinesof the formula (VI) are also suitable as such photoactive compounds, andare especially capable of releasing a chloride ion when subjected tosuitable photolytic conditions.

wherein

R₃₂, R₃₃ and R₃₄ are the same or different and independently of eachother selected from the group consisting of halogen, methyl, ethyl,linear or branched (C₃-C₁₂)alkyl, trichloromethyl, pentachloroethyl,linear or branched perhalo(C₃-C₁₂)alkyl, (C₆-C₁₀)aryl,(C₆-C₁₀)aryl(C₁-C₃)alkyl, perhalo(C₆-C₁₀)aryl,perhalo(C₆-C₁₀)arylperhalo(C₁-C₃)alkyl, substituted or unsubstitutedfive membered or six membered heteroaryl(C₂-C₄)alkenyl and substitutedor unsubstituted (C₆-C₁₀)aryl(C₂-C₄)alkenyl provided that one of R₃₂,R₃₃ and R₃₄ is trihalomethyl, pentahaloethyl, linear or branchedperhalo(C₃-C₁₂)alkyl. Specific examples of R₃₂, R₃₃ and R₃₄ includewithout any limitation chlorine, bromine, trichloromethyl,tribromomethyl, pentachloroethyl, pentabromoethyl, perchloropropyl,perbromopropyl, and the like.

Representative examples of the compounds of formula (V) may be listed asfollows:

Representative examples of the compound of formula (VI) without anlimitation may be enumerated as follows:

Advantageously, it has now been found that certain of the rutheniumcompounds of formula (II) or (III) does not require a photoactivecompound of formula (V) or a compound of formula (VI). Thus in someembodiments of this invention the component A of the composition of thiscontains a ruthenium compound of formula (II) or (III), and component Bof the composition of this invention contains a photoactive (orthermoactive) acid generators. Again, either or both components A and Bcan contain one or more monomers of formulae (I) and if necessary one ormore monomers of formula (IV) and/or one or more monomers of formula(VII).

In some embodiments the compounds of formula (V) can be activated atcertain wavelength of the electromagnetic radiation which can generallyrange from about 240 nm to 400 nm. Accordingly, any of the compoundswhich are active in this electromagnetic radiation can be employed inthe compositions of this invention which are stable to the 3Dfabrication methods. In some embodiments the wavelength of the radiationto activate the compounds of formula (V) is 260 nm. In some otherembodiments the wavelength of the radiation to activate the compounds offormula (V) is 310 nm. In yet some other embodiments the wavelength ofthe radiation to activate the compounds of formula (V) is 365 nm or 395nm, and so on.

However, any of the other known photoactive compounds which acceleratethe generation of photoacid and/or generate the chloride ion in order toactivate the latent catalysts, if needed, herein can also be used in thecomposition of this invention. All such compounds are part of thisinvention.

Any amount of latent catalyst and the compound of formula (V) or acompound of formula (VI) can be employed in the composition of thisinvention which will bring about the intended result. Generally, themolar ratio of monomer:latent catalyst:compound of formula (V) or acompound of formula (VI) is in the range of 10,000:1:1 to 5,000:1:1 orlower. In some other embodiments, the compound of formula (V) or acompound of formula (VI) is employed at higher level than the latentcatalyst, for example, such ranges may include monomer:latentcatalyst:photo active initiator is 10,000:1:2, 10,000:1:4 or higher. Insome other embodiments such monomer:latent catalyst:photo activeinitiator is 15,000:1:4, 20,000:1:4 or higher.

As noted, the composition of this invention further contains one or moreadditives selected from the group consisting of a photoactive acidgenerator, a thermal acid generator, and a mixture in any combinationthereof. In some embodiments the photoacid generator of the formula(VIII) is employed in the composition of this invention:Aryl₁-Hal^(⊕)-Aryl₂An^(⊖)  (VIII)Wherein Aryl₁ and Aryl₂ are the same or different and are independentlyselected from the group consisting of substituted or unsubstitutedphenyl, biphenyl and naphthyl; Hal is iodine or bromine; and An^(⊖) is aweakly coordinating anion (WCA) which is weakly coordinated to thecation complex. More specifically, the WCA anion functions as astabilizing anion to the cation complex. The WCA anion is relativelyinert in that it is non-oxidative, non-reducing, and non-nucleophilic.In general, the WCA can be selected from borates, phosphates, arsenates,antimonates, aluminates, boratobenzene anions, carborane, halocarboraneanions, sulfonamidate and sulfonates.

Representative examples of the compounds of formula (VIII) may be listedas follows:

Wherein n is an integer from 0 to 5; R₃₅ and R₃₆ are the same ordifferent and independently of each other selected from methyl, ethyl,linear or branched (C₃-C₂₀)alkyl, (C₃-C₁₂)cycloalkyl,(C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl,(C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy,(C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy,(C₆-C₁₀)aryloxy(C₁-C₃)alkyl, (C₆-C₁₀)-aryloxy, (C₆-C₁₀)-thioaryl and(C₆-C₁₀)-thioaryl-(C₆-C₁₀)diarylsulfonium salt. An^(⊖) is selected fromthe group consisting of Cl^(⊖), Br^(⊖), I^(⊖), BF₄ ^(⊖), B(C₆F₅)₄ ^(⊖),PF₆ ^(⊖), n-C₄F₉SO₃ ^(⊖), CF₃SO₃ ^(⊖) and p-CH₃(C₆H₄)—SO₃ ^(⊖).

It should further be noted that more than one R₃₅ and R₃₆ substituentcan be present in aforementioned compounds of formula (VIII₂) or(VIII₃). Interestingly, it has now been found that compounds of formula(VIII₁) where R₃₅ and R₃₆ are longer chain alkyl groups, such as forexample, (C₁₀H₂₁—C₁₃H₂₇)alkyl, provide certain benefits in that suchphotoacid generators are soluble in many of the monomers of formula (I)or monomers of formula (IV), thus avoiding any need to use solvent todissolve such photoacid generators and thus providing additionaladvantages.

Similarly, various other known sulfonium salts and quaternary ammoniumsalts can also be employed. A representative example of such sulfoniumsalt of formula (IX) is shown below:

Wherein n, An^(⊖), R₃₅ and R₃₆ are as defined above, and R₃₇ isindependently same as defined for R₃₅ and R₃₆.

Non-limiting examples of suitable additives that may be employed in thecomposition of this invention are listed below:

where R₃₅ and R₃₆ are the same or different and each independentlyselected from linear or branched (C₁₀-C₁₃)alkyl, commercially availableas Silcolease UV CATA 243 from Elkem; and

Various other photoactive (or thermoactive) acid generators are alsoknown in the art which may not be encompassed by the generic structuresshown above. All such photoacid (or thermoactive) acid generators canalso be used in the composition of this invention. Non-limiting examplesof such photoactive (or thermoactive) acid generators may be enumeratedas follows:

Another representative class of thermal acid generators is a variety ofquaternary ammonium salts, including halides, acetates,trifluoroacetates, phosphates, hexafluorophosphates,hexafuoroantimonates and sulfonate salts. For example, quaternaryammonium sulfonate salts may be generically represented by the followingformula:

wherein R₁₁, R₁₂, R₁₃ and R₁₄ are the same or different and eachindependently selected from the group consisting of methyl, ethyl,linear or branched (C₃-C₁₆)alkyl, perfluoro(C₁-C₁₂)alkyl, substituted orunsubstituted (C₆-C₁₀)aryl, substituted or unsubstituted(C₆-C₁₀)aryl(C₃-C₁₆)alkyl, (C₃-C₁₂)cycloalkyl or wherein any two of R₁₁,R₁₂, R₁₃ and R₁₄ taken together with the nitrogen atom to which they areattached form a (C₃-C₁₂)cyclic or (C₅-C₁₂)bicyclic ring; and

R₁₅ is selected from the group consisting of methyl, ethyl, linear orbranched (C₃-C₁₆)alkyl, perfluoro(C₁-C₁₂)alkyl, substituted orunsubstituted (C₆-C₁₀)aryl and substituted or unsubstituted(C₆-C₁₀)aryl(C₃-C₁₆)alkyl.

Non-limiting examples of such quaternary ammonium salts include withoutany limitation tetra-alkylammonium salts, such as for example,tetraethyl ammonium acetate, tetrabutylammonium chloride, and the like.Other representative quaternary ammonium salts include a variety ofsulfonate salts commercially available under the tradename K-PURE®quaternary ammonium blocked acids, from King Industries. Variousquaternary ammonium sulfonate salts can be employed including the saltsof dinonylnaphthalene disulfonic acid, dinonylnaphthalene sulfonic acid,para-toluene sulfonic acid, dodecylbenzene sulfonic acid, methanesulfonic acid, trifluoromethane sulfonic acid and perfluorobutanesulfonic acid. Representative examples of such quaternary ammoniumsulfonates include without any limitation N,N,N-trimethyl-N-benzyltriflate, N-benzyl-N,N-dimethyl-4-nitro-N-phenyl nonafluorobutanesulfonate, 4-methyl-N-benzyl-N,N-dimethyl-N-phenyl triflate,N-benzyl-N,N-dimethyl-N-phenyl triflate,4-methoxy-N-benzyl-N,N-dimethyl-N-phenyl triflate, and the like. A fewof these quaternary ammonium salts are available commercially, forexample, TAG-2678, TAG-2689 and TAG-2700, all from King Industries.

Another class of quaternary salts includes various pyridinium sulfonatesalts of the formula shown below. Such pyridinium salts may also includeother anions such as the ones mentioned above, i.e., halides, acetates,trifluoroacetates, phosphates, hexafluorophosphates,hexafuoroantimonates and the like.

wherein n is an integer from 0 to 5;

R₁₅ is as defined above;

R₁₆ selected from the group consisting of methyl, ethyl, linear orbranched

-   -   (C₃-C₁₆)alkyl, perfluoro(C₁-C₁₂)alkyl and substituted or        unsubstituted    -   (C₆-C₁₀)aryl and substituted or unsubstituted        (C₆-C₁₀)aryl(C₃-C₁₆)alkyl; and

R₁₇ is independently selected from the group consisting of methyl,ethyl, linear or branched (C₃-C₁₆)alkyl, perfluoro(C₁-C₁₂)alkyl,substituted or unsubstituted (C₆-C₁₀)aryl and substituted orunsubstituted (C₆-C₁₀)aryl(C₃-C₁₆)alkyl.

Representative examples of such pyridinium salts include without anylimitation pyridinium triflate, 1-(4-methoxyphenyl)methyl-pyridiniumtriflate, and the like.

However, any of the other known photoactive or thermally activecompounds which generate the activator for the latent catalysts employedherein can also be used in the composition of this invention. All suchcompounds are part of this invention.

Any of the amounts of photoactive (or thermoactive) acid generators canbe employed herein that would bring about the intended result.Generally, such amounts varies from twice the molar amounts to that ofthe ruthenium compound to three or four times the molar amounts of theruthenium compound as employed herein. That is, molar ratio oforgano-ruthenium compound of formula (II) or (III) to photo acidgenerator is generally 1:2 or 1:3 or 1:4 or higher. However, in somesituations equimolar amounts of ruthenium compound and the photoacidgenerator may also be suitable.

Advantageously, it has further been found that the composition accordingto this invention forms a substantially three dimensional object whenmass polymerized, generally, when exposed to suitable radiation at awavelength in the range from 260 nm to 400 nm. That is to say, when thecomposition of this invention is exposed to suitable radiation, themonomers undergo mass polymerization to form solid objects under routine3D printing technologies.

In some other embodiments the compositions of this invention can also bephotopatterned by image-wise exposing the compositions of this inventionto a suitable radiation. Similarly, the compositions of this inventionare also useful for forming photo imprint of a suitable substrate. Thatis, the composition of this invention can be employed in a variety ofphoto or thermal induced nanoimprint lithography (NIL). For example, apatterned digital video disk (DVD) can be replicated by pouring ontosuch exposed patterned DVD a combined mixture of component A andcomponent B of this invention and then subjecting the coated surface toa suitable radiation. Upon such exposure the solidified film can bepeeled off from the substrate which will have a reproduction of theoriginal disk as fully described in specific example that follows.

Accordingly, in some embodiments the composition of this inventionundergoes mass polymerization when both components A and B are mixed andexposed to suitable UV irradiation which is substantially free of anymonomer or volatile oligomeric product. The resulting solid form takesshape of the substrate and/or can be photopatterned by imagewiseexposure and developing the image formed therefrom.

It has also been found that various other viscosity modifiers that arecompatible with the compositions of this invention can also be employedin order to modulate the viscosity of the composition before subjectingit to the mass polymerization conditions. Suitable examples of suchviscosity modifiers include transparent polymers such as for examplepolystyrene, polyesters (polyethylene terphthalate, PET), and the like.

Accordingly, in some embodiments of this invention there is provided twocomponent composition comprising in component A one or more monomers offormula (I), optionally one or more monomers of formula (IV), a latentorganoruthenium catalyst of formula (II) or (III) and a compound offormula (V) as described hereinabove. And in component B a solution of aphotoacid generator in a suitable solvent and/or one or more monomers offormulae (I), (IV) or (VII). Any of the monomers of formula (I) asdescribed hereinabove can be used in this aspect of the invention,optionally in combination with one or more monomers of formula (IV) or(VII). The monomers of formula (I) featuring a viscosity below 50centipoise are generally employed. When more than two monomers offormula (I) are employed the first monomer is completely miscible withthe second monomer and forms a clear solution. When the composition isexposed to suitable irradiation and fabricated under suitable 3Dprinting conditions forms a 3D object.

In another embodiment of this invention, the composition of thisinvention encompasses component A containing a mixture of5-phenethylbicyclo[2.2.1]hept-2-ene (PENB),1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-tricyclohexylphosphine-rutheniumcarbide dichloride (Ru-1) and 1-chloro-4-propoxy-9H-thioxanthen-9-one(CPTX), and component B containing a solution oftolylcumyliodonium-tetrakis pentafluorophenylborate (Rhodorsil 2074) intoluene.

In another embodiment of this invention, the composition of thisinvention encompasses component A containing a mixture of5-phenethylbicyclo[2.2.1]hept-2-ene (PENB),1,3-bis(2,6-diisopropylphenylimidazolidin-2-ylidene)-tricyclohexylphosphine-rutheniumcarbide dichloride (Ru-3) and 1-chloro-4-propoxy-9H-thioxanthen-9-one(CPTX), and component B containing a solution oftolylcumyliodonium-tetrakis pentafluorophenylborate (Rhodorsil 2074) intoluene.

In another embodiment of this invention, the composition of thisinvention encompasses component A containing a mixture of5-phenethylbicyclo[2.2.1]hept-2-ene (PENB),1-(2,6-diethylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene-triisopropylphosphineruthenium carbide dichloride (Ru-5) and1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX), and component Bcontaining a solution of tolylcumyliodonium-tetrakispentafluorophenylborate (Rhodorsil 2074) in toluene.

In another embodiment of this invention, the composition of thisinvention encompasses component A containing a mixture of5-phenethylbicyclo[2.2.1]hept-2-ene (PENB),1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene-triisopropylphosphineruthenium carbide dichloride (Ru-6) and1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX), and component Bcontaining a solution of tolylcumyliodonium-tetrakispentafluorophenylborate (Rhodorsil 2074) in toluene.

In another embodiment of this invention, the composition of thisinvention encompasses component A containing a mixture of5-phenethylbicyclo[2.2.1]hept-2-ene (PENB),1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-tricyclohexylphosphine-rutheniumcarbide dichloride (Ru-1) and 1-chloro-4-propoxy-9H-thioxanthen-9-one(CPTX), and component B containing a mixture of5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene(NBEtO-2-PhPh) and tolylcumyliodonium-tetrakis pentafluorophenylboratetolylcumyliodonium-tetrakis pentafluorophenylborate (Rhodorsil 2074).

In another embodiment of this invention, the composition of thisinvention encompasses component A containing a mixture of5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), dicyclopentadiene (DCPD),1-(2,6-diethylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene-triisopropylphosphineruthenium carbide dichloride (Ru-5) and1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX), and component Bcontaining a mixture of5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene(NBEtO-2-PhPh) and tolylcumyliodonium-tetrakis pentafluorophenylborate(Rhodorsil 2074).

In another embodiment of this invention, the composition of thisinvention encompasses component A containing a mixture of5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), dicyclopentadiene (DCPD),1,3-bis(2,6-diisopropylphenylimidazolidin-2-ylidene)-tricyclohexylphosphine-rutheniumcarbide dichloride (Ru-6) and 1-chloro-4-propoxy-9H-thioxanthen-9-one(CPTX), and component B containing a mixture of5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene(NBEtO-2-PhPh) and tolylcumyliodonium-tetrakis pentafluorophenylborate(Rhodorsil 2074).

In another embodiment of this invention, the composition of thisinvention encompasses component A containing a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD),3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene(CPD3),1-(2,6-diethylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene-triisopropylphosphineruthenium carbide dichloride (Ru-5) and 4-isopropylthioxanthone (ITX),and component B containing a mixture of2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene(HexylTD),3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene(CPD3) and bis(4-decylphenyl)iodonium-tetrakis pentafluorophenylborate.

In a further aspect of this invention there is also provided a kit forforming a three dimensional object. There is dispensed in this kitcomponent A and component B of the composition of this invention.Accordingly, in some embodiments there is provided a kit in which thereis dispensed in two separate components one or more monomers of formula(I), optionally one or more monomers of formula (IV) and/or one or moremonomers of formula (VII) and a compound of formula (V), so as to obtaina desirable result and/or for intended purpose. Further, said kitcomprises a latent catalyst and photo (or thermoactive) acid generatoras described herein. The monomers of formulae (I), (IV) or (VII) are theones as described hereinabove.

In some embodiments, the aforementioned kit encompasses two or moremonomers of formula (I) distinct from one another as describedhereinabove. In some other embodiments the kit of this inventionencompasses at least two monomers wherein first monomer facilitatesdissolution of the second monomer and/or the latent catalyst and theadditives as described hereinabove. Any of the monomers of formula (I)as described herein can be used in this embodiment. The molar ratio offirst and the second monomer of formula (I) contained in thesecomponents can vary and may range from 1:99 to 99:1, or 10:90 to 90:10,20:80 to 80:20, 30:70 to 70:30, 60:40 to 40:60 or 50:50, and so on. Insome other embodiments the kit may encompass a composition whereindispensed more than two monomers of formula (I), each distinct from oneanother. Further, as noted the first monomer of formula (I) iscompletely soluble in the second monomer of formula (I) to form a clearsolution at room temperature. In some embodiments the monomer mixturemay become a clear solution at slightly elevated temperature, such asfor example, 30° C. or 40° C. or 50° C., before they undergo masspolymerization. In another aspect of this embodiment of this inventionthe composition of this invention undergoes mass polymerization whenexposed to a suitable radiation for a sufficient length of time to forma 3D object. That is to say that the composition of this invention whenused in a suitable 3D printing system capable of exposing to a suitableradiation forms a desirable 3D object. Generally, as already notedabove, such polymerization can take place when exposed to suitableradiation at a wavelength from about 260 nm to 400 nm or higher. Theexposure can be at stages from 260 nm to 400 nm or at suitablewavelengths as described herein. By practice of this invention it is nowpossible to form 3D objects using any of the known 3D printingtechnologies.

In some embodiments the kit according to this invention contains atleast two monomers of formula (I) distinct from one another, wherein onemonomer is completely soluble in the other monomer, and when saidcomposition is exposed to radiation at 395 nm for a sufficient length oftime it forms a three dimensional object.

In some embodiments, the kit as described herein encompasses variouscompositions as described herein.

As noted, the compositions of this invention can be used in any of theknown three dimensional (3D) printing technologies and other printingtechnologies. A few of the 3D printing procedures known in the artinclude continuous liquid interface production (CLIP), layer by layerapproach (LBL), inkjet printing and frontal polymerization method, suchas frontal ring open metathesis (FROMP) technique, see for exampleRobertson et al., Nature, Vol. 557, 223-227 (2018).

In a CLIP approach, a 3D object is continuously formed by projecting acontinuous sequence of UV images (generated by a digitallight-processing (DLP) imaging unit or a laser to generate the part)through an oxygen permeable, UV-transparent window below a liquid resinbath containing the compositions of this invention. The dead zonecreated above the window maintains a liquid interface below theadvancing part. Above the dead zone, the curing part is continuouslydrawn out of the resin bath. The suction forces resulted due to thisdrawing replenishes the resin bath at the same time. In this way variousparts of different dimensions up to several centimeters with partresolution lower than 100 microns can be fabricated.

In a 3D inkjet printing technology, the compositions of this inventioncan be used as photopolymerizable ink compositions to form lines andvias on a substrate, typically on a silicon wafer. A wide variety ofparts having utility in electronic and optoelectronic applications canthus be manufactured using the compositions of this invention. Nonlimiting examples of such applications include manufacturing of OLEDdevices on a variety of substrates, which can be produced substantiallyin a particle free environment at high yields. The compositions of thisinvention may act as organic encapsulant layers and/or as fillermaterials in some of such OLED devices.

Accordingly, in yet another aspect of this invention there is furtherprovided a method of forming a three dimensional object comprising:

providing a homogeneous clear composition in a suitable container, thecomposition comprising one or more monomers of formula (I), a latentcatalyst and a compound of formula (V) or a compound of formula (VI),optionally in combination with one or more monomers of formula (IV);

exposing to suitable UV radiation while drawing the composition from thecontainer, and

forming a three dimensional object.

The 3D objects formed in accordance with the method of this inventionexhibit excellent thermal and mechanical properties. In general, theproperties of these objects can be tailored to intended end use. Forexample, the thermal properties of the 3D objects can be tailored to bestable up to 180° C. or higher depending upon the types of monomers offormula (I) in combination with monomers of formula (IV) employed toform such 3D objects. Similarly, the mechanical properties can also betailored to desired mechanical properties simply by the selection ofsuitable monomers as described herein. In general, by tailoring theproper choice of monomers the parts possessing very high impact strengthcan be fabricated.

Accordingly, in some of the embodiments of this invention there is alsoprovided a three dimensional object comprising the composition of thisinvention which exhibits excellent thermal and mechanical properties.

In yet some other embodiments the composition of this invention can alsobe used in a variety of thermal and/or photo induced nanoimprintlithography (NIL), such as for example, UV-NIL. For instance, thecompositions of this invention can be used in a variety of photocurableimprint technology. Typically in such applications, the component A andcomponent B of this invention are mixed together and suitably placed ona substrate, which is then covered by a suitable stamp and exposed toradiation so as to allow the composition of this invention to cure to asolid. The stamp is then released to obtain the nano-imprinted film.

The following examples are detailed descriptions of methods ofpreparation and use of certain compounds/monomers, polymers andcompositions of the present invention. The detailed preparations fallwithin the scope of, and serve to exemplify, the more generallydescribed methods of preparation set forth above. The examples arepresented for illustrative purposes only, and are not intended as arestriction on the scope of the invention. As used in the examples andthroughout the specification the ratio of monomer to catalyst is basedon a mole to mole basis.

EXAMPLES

The following abbreviations have been used hereinbefore and hereafter indescribing some of the compounds, instruments and/or methods employed toillustrate certain of the embodiments of this invention:

PENB—5-phenethylbicyclo[2.2.1]hept-2-ene;NBEtO-2-PhPh-5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene;HexylTD—2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene;DCPD—dicyclopentadiene;CPD3—3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene;Ru-1—1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-tricyclohexylphosphine-rutheniumcarbide dichloride;Ru-3—1,3-bis(2,6-diisopropylphenylimidazolidin-2-ylidene)-tricyclohexylphosphine-rutheniumcarbide dichloride;Ru-5—1-(2,6-diethylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene-triisopropylphosphineruthenium carbide dichloride;Ru-6—1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene-triisopropylphosphineruthenium carbide dichloride;CPTX—1-chloro-4-propoxy-9H-thioxanthen-9-one;ITX—4-isopropylthioxanthone; Rhodorsil 2074—tolylcumyliodonium-tetrakispentafluorophenylborate; Silcolease UV CATA 243—dialkyliodonium-tetrakispentafluorophenylborate as described herein; DSC—differential scanningcalorimetry; TGA—thermogravimetric analysis; UV-NIL—ultravioletnanoimprint lithography.

Various monomers as used herein are either commercially available or canbe readily prepared following the procedures as described in U.S. Pat.No. 9,944,818.

The following Examples demonstrate that the compositions of thisinvention are quite stable at ambient temperature conditions and even upto 35° C. for several days and can very readily be mass polymerized byexposing to a suitable radiation as specified below.

Example 1 Mass Polymerization of PENB

Component A of this invention was first prepared in a glass bottle asfollows: Ru-6 (1 molar part) and CPTX (2 molar part) were dissolved inPENB (10,000 molar parts) to form a clear solution. Component B of thisinvention was then prepared in a separate glass bottle as follows:Rhodorsil 2074 (2 molar parts) was dissolved in sufficient toluene(about 1 weight percent of total formulation). Both solutions were thenmixed together and purged with nitrogen for 2 hours. The solution was UVlight exposed (UV LED flash light 395 nm for 3 min). The solution turnedto a solid indicating the monomer was fully polymerized, as confirmed byboth UV/DSC and TGA. The residue percentage from isothermal TGA (1 h at100° C.) after UV exposure was >99%.

Examples 2-3 Mass Polymerization of PENB

The procedures of Example 1 were substantially repeated in theseExamples 2 and 3 except that various different ruthenium carbidecatalysts as listed in Table 1 were employed. The monomer and catalystloading used in each of these Examples 2 and 3, and the heat of reactionas measured from the UV DSC are summarized in Table 1.

TABLE 1 Ru-complex Example Monomer loading, UV DSC, No. (molar parts)(molar parts) J/g 2 PENB Ru-3 220 (10,000) (1) 3 PENB Ru-5 275 (10,000)(1)

Examples 4-5 Mass Polymerization of Various Monomers

The procedures of Example 1 were substantially repeated in theseExamples 4 and 5 except that various different monomers and catalysts aslisted in Table 2 were employed. NBEtO-2-PhPh itself served as a solventto dissolve Rhodorsil 2074 in these Examples 4-5, instead of toluene.The monomers used in each of these Examples 4-5, catalyst loading,Rhodorsil 2074 and heat of reaction from UV DSC are summarized in Table2.

TABLE 2 Ru-complex Example Monomers loading, UV DSC, No. (molar parts)(molar parts) J/g 4 PENB/NBEtO-2-PhPh Ru-1 260 90/10 molar ratio (1)(10,000) 5 DCPD/PENB/NBEtO-2-PhPh Ru-5 250 85/5/10 molar ratio (1)(10,000)

Example 6

The procedures of Example 5 was substantially repeated in this Example 6except that ITX was used instead of CPTX. Total heat of reaction from UVDSC was 400 J/g indicating substantial completion of polymerizationreaction.

Examples 7-9

The procedures of Example 1 was substantially repeated in these Examples8 to 10 except that various different catalysts were employed as listedin Table 3. None of these compositions contained CPTX. The compositionswere exposed to UV ABM Mask Aligner Broadband. The results aresummarized in Table 3. It is evident from these results that thecompositions of this invention are still active without CPTX, i.e., thephotosensitizers.

TABLE 3 Example Visual appearance No. Ru-complex after UV exposure 7Ru-3 solid 8 Ru-5 solid 9 Ru-6 solid

Examples 10-11 Component A Shelf Life Studies

Component A was prepared in separate glass bottles containing variousRu-catalysts (1 molar part) dissolved in PENB (10,000 molar parts) toform a clear solution as listed in Table 4. Viscosity changes for eachof these Examples 10-11 at room temperature were monitored over a periodof seven days and are summarized in Table 4. As summarized in Table 4,component A of Examples 10 and 11 were in liquid form with more or lesssimilar viscosities even at the end of seven days.

TABLE 4 Example Ru- Viscosity at Viscosity at Viscosity at No. complexday 0, cPa day 1, cPa day 7, cPa 10 Ru-3 7.2 8.4 9.2 11 Ru-5 7.2 7.3 8.1

Example 12 Formation of 3D Objects

In a glass bottle, Ru-5 (0.0041 g, 0.0067 mmol), Rhodorsil (0.0136 g,0.00134 mmol) and CPTX (0.0041 g, 0.0134 mmol) were dissolved inDCPD/NBEtO-2-PhPh (90/10 mole ratio, 10 g, 67.56 mmol) to form a clearsolution, the monomer to catalyst ratio was at 10,000:1. The solutionwas kept overnight at r.t. and had become viscous. This viscous solutionwas then filled into a motorized syringe and slowly pushed out of thenozzle at a steady rate while exposing the nozzle to UV light (LED 270mW/cm², 395 nm), the liquid coming out of the nozzle immediatelysolidified forming a 3D object.

Example 13 Shelf Life/Reactivity Studies

Two separate Component A were prepared in two separate glass bottles,each of which containing Ru-5 (1 molar part) and CPTX (2 molar parts)dissolved in PENB (5,000 molar parts) to form a clear solution.Similarly, two separate Component B were prepared in two separate glassbottles, each of which contained Rhodorsil 2074 (2 molar parts)dissolved in PENB/NBEtO-2-PhPh (4,000/1,000 molar parts). BothComponents A and B kept separately were purged with nitrogen for 2hours. The reactivity of one of Component A and one of Component B waschecked by mixing them together immediately after purging them overnitrogen for 2 hours using UV DSC (30° C., 250 mW/cm², 4 sec of 400 nmUV light), the heat of reaction was measured to be 400 J/g. The otherset of Component A and Component B were stored at room temperature forten days during which time no viscosity change was observed. Thereactivity of these two components were checked at this time by mixingthem together in the same fashion as before using UV DSC (30° C., 250mW/cm², 4 sec of 400 nm UV light), the heat of reaction was measured tobe 389 J/g. This clearly demonstrates that the two componentcompositions of this invention is not only stable at ambient conditionsbut also retains the same reactivity after storage for several days whenmixed together and subjected to suitable radiation.

Example 14 Mass Polymerization of HexylTD/CPD3

In a glass bottle, Component A was prepared by dissolving Ru-5 (1 molarpart) and ITX (8 molar parts) in HexylTD/CPD3 (9,000/1,000 molar parts)to form a clear solution. Component B was similarly formed by dissolvingSilcolease UV CATA 243 (4 molar parts) in HexylTD/CPD3 (9,000/1,000molar parts) to form a clear solution and both components were purgedwith nitrogen for 5 hours. Both Component A and B were then mixedtogether and exposed to UV DSC (30° C., 250 mW/cm², 4 sec of 400 nm UVlight). The heat of reaction was measured to be 432 J/g indicatingcomplete polymerization of the monomers.

Example 15 UV-NIL of DCPD/NBEtO-2-PhPh Composition

In a glass bottle, Component A was prepared by dissolving Ru-5 (1 molarpart) and ITX (2 molar parts) in DCPD (8,000 molar parts) to form aclear solution. In a separate glass bottle, Component B was prepared bydissolving Rhodorsil 2074 (2 molar parts) in NBEtO-2-PhPh (2,000 molarparts). Both Component A and Component B were then mixed together andpurged with nitrogen for 2 hours. A DVD (Verbatim) was separated using arazor blade and cleaned with methanol to expose the channel patternedsurface. FIG. 1 shows the optical micrograph of the exposed channelpatterns of the DVD. The mixed solution of Components A and B was thenpoured on a glass substrate and covered with the exposed channelpatterned surface of the DVD facing the solution. The sandwiched glasssubstrate and the DVD was then exposed to UV light (500 mW/cm² for 4seconds). The cured film was peeled off from the DVD and the glasssubstrate, and characterized by optical microscopy. FIG. 2 shows thechannel surface imprinted on the film formed from the composition ofthis invention. This clearly demonstrates that the composition of thisinvention can be used for forming nanoimprints.

The following Comparative Examples 1 to 3 illustrate that a photoacidgenerators are needed to effectively activate the ruthenium carbidecatalysts. In some of these Comparative Examples use of photosensitizeralone is also found to be ineffective to cause polymerization.

Comparative Example 1

The procedures of Example 5 was substantially repeated in thisComparative Example 1 except that photosensitizer was not used in theformulation. Total heat of reaction from UV DSC was less than 10 J/g.

Comparative Example 2

The procedures of Example 4 was substantially repeated in thisComparative Example 2 except that Rhodorsil 2074 and photosensitizerwere not used in the formulation. Total heat of reaction from UV DSC was60 J/g. It indicates that the catalyst Ru-1 became moderately activeunder these conditions, however, this composition also exhibited poorshelf life stability.

Comparative Example 3

The procedures of Example 12 were substantially repeated in thisComparative Example 3 except that CPTX was not added to the solution.The solution was kept overnight at r.t. but viscosity was not changed.The solution remained in a liquid form and dripped from the nozzleduring UV light exposure.

Although the invention has been illustrated by certain of the precedingexamples, it is not to be construed as being limited thereby; butrather, the invention encompasses the generic area as hereinbeforedisclosed. Various modifications and embodiments can be made withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A two component composition comprising componentA and component B, wherein component A contains a latentorgano-ruthenium carbide catalyst and component B contains a photoactiveor a thermoactive acid generator and either of the component A or thecomponent B further comprising: a) one or more monomers of formula (I):

wherein: m is an integer 0, 1 or 2;

is a single bond or a double bond; R₁, R₂, R₃ and R₄ are the same ordifferent and each independently selected from the group consisting ofhydrogen, halogen, methyl, ethyl, linear or branched (C₃-C₁₆)alkyl,(C₂-C₁₆)alkenyl, perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl,(C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl, methoxy, ethoxy, linear orbranched (C₃-C₁₆)alkoxy, (C₂-C₆)acyl, (C₂-C₆)acyloxy,perfluoro(C₆-C₁₄)aryl, perfluoro(C₆-C₁₄)aryl(C₁-C₃)alkyl,(C₆-C₁₄)aryloxy, (C₆-C₁₄)aryl(C₁-C₆)alkoxy, tri(C₁-C₆)alkoxysilyl and agroup of formula (A):—Z-Aryl  (A) wherein: Z is a bond or a group selected from the groupconsisting of: (CR₅R₆)_(a), O(CR₅R₆)_(a), (CR₅R₆)_(a)O,(CR₅R₆)_(a)—O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O—(SiR₅R₆)_(b),(CR₅R₆)_(a)—(CO)O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O(CO)—(CR₅R₆)_(b),(CR₅R₆)_(a)—(CO)—(CR₅R₆)_(b), where a and b are integers which may bethe same or different and each independently is 1 to 12; R₅ and R₆ arethe same or different and each independently selected from the groupconsisting of hydrogen, methyl ethyl, linear or branched (C₃-C₆)alkyl,methoxy, ethoxy, linear or branched (C₃-C₆)alkyloxy, (C₂-C₆)acyl,(C₂-C₆)acyloxy, phenyl and phenoxy; Aryl is selected from the groupconsisting of phenyl, biphenyl and naphthyl, where the aryl isoptionally substituted with one or more of groups selected from thegroup consisting of methyl, ethyl, linear or branched (C₃-C₆)alkyl,hydroxy, methoxy, ethoxy, linear or branched (C₃-C₆)alkyloxy,(C₂-C₆)acyl, (C₂-C₆)acyloxy, phenyl and phenoxy; or one of R₁ or R₂taken together with one of R₃ or R₄ and the carbon atoms to which theyare attached to form a (C₅-C₇)carbocyclic ring optionally containing oneor more double bonds; and b) a photoactive compound selected from thegroup consisting of: a compound of the formula (V):

wherein X is hydrogen or chlorine; R₃₀ and R₃₁ are the same or differentand independently of each other selected from the group consisting ofhydrogen, chlorine, methyl, ethyl, linear or branched (C₃-C₁₂)alkyl,(C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl,(C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₁-C₁₂)alkoxy,(C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy,(C₆-C₁₀)aryloxy(C₁-C₃)alkyl and (C₆-C₁₀)-aryloxy; and a compound of theformula (VI):

wherein R₃₂, R₃₃ and R₃₄ are the same or different and independently ofeach other selected from the group consisting of halogen, methyl, ethyl,linear or branched (C₃-C₁₂)alkyl, trichloromethyl, pentachloroethyl,linear or branched perhalo(C₃-C₁₂)alkyl, (C₆-C₁₀)aryl,(C₆-C₁₀)aryl(C₁-C₃)alkyl, perhalo(C₆-C₁₀)aryl,perhalo(C₆-C₁₀)arylperhalo(C₁-C₃)alkyl, substituted or unsubstitutedfive membered or six membered heteroaryl(C₂-C₄)alkenyl and substitutedor unsubstituted (C₆-C₁₀)aryl(C₂-C₄)alkenyl provided that one of R₃₂,R₃₃ and R₃₄ is trihalomethyl, pentahaloethyl, linear or branchedperhalo(C₃-C₁₂)alkyl; and wherein said latent organo-ruthenium carbidecatalyst is of formula (II):

wherein: L is PR₃, where R is independently selected from the groupconsisting of isopropyl, sec-butyl, tert-butyl, cyclohexyl,bicyclo(C₅-C₁₀)alkyl, phenyl, benzyl, isopropoxy, sec-butoxy,tert-butoxy, cyclohexyloxy, phenoxy and benzyloxy; R₇ is selected fromthe group consisting of methyl, ethyl, isopropyl, sec-butyl, tert-butyl,substituted or unsubstituted cyclohexyl, substituted or unsubstitutedphenyl, substituted or unsubstituted biphenyl and substituted orunsubstituted naphthyl; Ar₁ is selected from the group consisting ofsubstituted or unsubstituted phenyl, substituted or unsubstitutedbiphenyl and substituted or unsubstituted naphthyl; wherein substituentsare selected from the group consisting of methyl, ethyl, iso-propyl,tert-butyl and phenyl; and wherein said component A and component B arein a clear liquid form having a viscosity below 100 centipoise at 25° C.2. The composition according to claim 1, wherein either of the componentA or the component B further comprising one or more monomers of formula(IV):

wherein R₁₆ and R₁₇ are the same or different and each independentlyselected from the group consisting of hydrogen, methyl ethyl, linear orbranched (C₃-C₆)alkyl, methoxy, ethoxy, linear or branched(C₃-C₆)alkyloxy, acetoxy, (C₂-C₆)acyl, phenyl and phenoxy; or R₁₆ takentogether with R₁₇ and the carbon atoms to which they are attached toform a (C₅-C₇)carbocyclic ring optionally containing one or more doublebonds; R₁₈ is hydrogen, halogen, methyl, ethyl, linear or branched(C₃-C₁₆)alkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₆)alkyl, hydroxy, methoxy,ethoxy, linear or branched (C₃-C₁₆)alkoxy, (C₆-C₁₀)aryloxy,(C₆-C₁₀)aryl(C₁-C₆)alkoxy, —O(CO)R₁₉ and —O(CO)OR₁₉, where R₁₉ ismethyl, ethyl, linear or branched (C₃-C₁₆)alkyl, (C₆-C₁₀)aryl and(C₆-C₁₀)aryl(C₁-C₆)alkyl.
 3. The composition according to claim 1,wherein either of the component A or the component B comprising firstand second monomer of formula (I) distinct from each other and one ofsaid first and second monomers having a viscosity below 50 centipoise at25° C., and wherein said first monomer is completely miscible with saidsecond monomer to form a clear solution.
 4. The composition according toclaim 1, wherein said composition comprising a monomer of formula (I)wherein m is 1 and each of R₁, R₂, R₃ and R₄ are hydrogen.
 5. Thecomposition according to claim 1, wherein said composition comprisingfirst and second monomer of formula (I) distinct from each other,wherein said first monomer is of formula (I) wherein m is 1 and each ofR₁, R₂, R₃ and R₄ are hydrogen; and wherein said second monomer is offormula (I) wherein m is 0, R₁ is decyl and each of R₂, R₃ and R₄ arehydrogen.
 6. The composition according to claim 1, wherein the monomerof formula (I) is selected from the group consisting of:


7. The composition according to claim 2, wherein one or more monomers offormula (IV) is selected from the group consisting of:


8. The composition according to claim 2, wherein said one or moremonomer of formula (I) is selected from the group consisting of:tetracyclododecene (TD); 5-butylbicyclo[2.2.1]hept-2-ene (BuNB);5-hexylbicyclo[2.2.1]hept-2-ene (HexylNB);5-decylbicyclo[2.2.1]hept-2-ene (DecylNB);5-phenethylbicyclo[2.2.1]hept-2-ene (PENB);5-(2-([1,1′-biphenyl]-4-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene; and5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene(NBEtO-2-PhPh); and wherein said monomer of formula (IV) isdicyclopentadiene (DCPD); and mixtures in any combination thereof. 9.The composition according to claim 1, wherein the latentorgano-ruthenium carbide catalyst of formula (II) is having: L is PR₃,where R is independently selected from the group consisting ofisopropyl, sec-butyl, tert-butyl, cyclohexyl and phenyl; Ar₁ and R₇ arethe same or different and each independently of each other selected fromthe group consisting of 2,4-dimethylphenyl, 2,4-diethylphenyl,2,4-diisopropylphenyl and 2,4,6-trimethylphenyl.
 10. The compositionaccording to claim 1, wherein the organo-ruthenium carbide catalyst offormula (II) is selected from the group consisting of:


11. The composition according to claim 1, wherein the compositioncomprises a photoactive compound which is a compound of the formula (V):

wherein X is hydrogen or chlorine; R₃₀ and R₃₁ are the same or differentand independently of each other selected from the group consisting ofhydrogen, chlorine, methyl, ethyl, isopropyl, methoxy, ethoxy, propoxyand phenoxy.
 12. The composition according to claim 11, wherein thephotoactive compound is selected from the group consisting of:


13. The composition according to claim 1, wherein the photoactive orthermoactive acid generator is of the formula (VIII₁) or of the formula(IX):

wherein n is an integer from 0 to 5; An^(⊕) is selected from the groupconsisting of Cl^(⊕), Br^(⊕), I^(⊕), BF₄ ^(⊕), B(C₆F₅)₄ ^(⊕), PF₆ ^(⊕),n-C₄F₉SO₃ ^(⊕), CF₃SO₃ ^(⊕) and p-CH₃(C₆H₄)—SO₃ ^(⊕); R₃₅, R₃₆ and R₃₇are the same or different and independently of each other selected fromthe group consisting of chlorine, methyl, ethyl, linear or branched(C₃-C₂₀)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl,(C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl,(C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy,(C₇-C₁₄)tricycloalkoxy, (C₆-C₁₀)aryloxy(C₁-C₃)alkyl, (C₆-C₁₀)-aryloxy,(C₆-C₁₀)-thioaryl and (C₆-C₁₀)-thioaryl-(C₆-C₁₀)diarylsulfonium salt.14. The composition according to claim 13, wherein the photoactive orthermoactive acid generator is selected from the group consisting of:

where R₃₅ and R₃₆ are the same or different and each independentlyselected from linear or branched (C₁₀-C₁₃)alkyl; and


15. The composition according to claim 1, which is selected from thegroup consisting of: component A containing a mixture of5-phenethylbicyclo[2.2.1]hept-2-ene,1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-tricyclohexylphosphine-rutheniumcarbide dichloride and 1-chloro-4-propoxy-9H-thioxanthen-9-one, andcomponent B containing tolylcumyliodonium-tetrakispentafluorophenylborate and toluene; component A containing a mixture of5-phenethylbicyclo[2.2.1]hept-2-ene,1,3-bis(2,6-diisopropylphenylimidazolidin-2-ylidene)-tricyclohexylphosphine-rutheniumcarbide dichloride and 1-chloro-4-propoxy-9H-thioxanthen-9-one, andcomponent B containing a mixture of tolylcumyliodonium-tetrakispentafluorophenylborate and toluene; component A containing a mixture of5-phenethylbicyclo[2.2.1]hept-2-ene,1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-tricyclohexylphosphine-rutheniumcarbide dichloride and 1-chloro-4-propoxy-9H-thioxanthen-9-one, andcomponent B containing a mixture of5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene andtolylcumyliodonium-tetrakis pentafluorophenylborate; and component Acontaining a mixture of 5-phenethylbicyclo[2.2.1]hept-2-ene,dicyclopentadiene,1,3-bis(2,6-diisopropylphenylimidazolidin-2-ylidene)-tricyclohexylphosphine-rutheniumcarbide dichloride and 1-chloro-4-propoxy-9H-thioxanthen-9-one; andcomponent B containing a mixture of tolylcumyliodonium-tetrakispentafluorophenylborate and5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene.
 16. A kitfor forming a three dimensional object comprising component A andcomponent B, wherein component A contains a latent organo-rutheniumcarbide catalyst and component B contains a photoactive or athermoactive acid generator and either of the component A or thecomponent B further comprising: a) one or more monomers of formula (I):

wherein: m is an integer 0, 1 or 2;

is a single bond or a double bond; R₁, R₂, R₃ and R₄ are the same ordifferent and each independently selected from the group consisting ofhydrogen, halogen, methyl, ethyl, linear or branched (C₃-C₁₆)alkyl,(C₂-C₁₆)alkenyl, perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl,(C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl, methoxy, ethoxy, linear orbranched (C₃-C₁₆)alkoxy, (C₂-C₆)acyl, (C₂-C₆)acyloxy, (C₆-C₁₄)aryl,(C₆-C₁₄)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₄)aryl,perfluoro(C₆-C₁₄)aryl(C₁-C₃)alkyl, (C₆-C₁₄)aryloxy,(C₆-C₁₄)aryl(C₁-C₆)alkoxy, tri(C₁-C₆)alkoxysilyl and a group of formula(A):—Z-Aryl  (A) wherein: Z is a bond or a group selected from the groupconsisting of: (CR₅R₆)_(a), O(CR₅R₆)_(a), (CR₅R₆)_(a)O,(CR₅R₆)_(a)—O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O—(SiR₅R₆)_(b),(CR₅R₆)_(a)—(CO)O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O(CO)—(CR₅R₆)_(b),(CR₅R₆)_(a)—(CO)—(CR₅R₆)_(b), where a and b are integers which may bethe same or different and each independently is 1 to 12; R₅ and R₆ arethe same or different and each independently selected from the groupconsisting of hydrogen, methyl ethyl, linear or branched (C₃-C₆)alkyl,methoxy, ethoxy, linear or branched (C₃-C₆)alkyloxy, (C₂-C₆)acyl,(C₂-C₆)acyloxy, phenyl and phenoxy; Aryl is phenyl or phenyl substitutedwith one or more of groups selected from the group consisting of methyl,ethyl, linear or branched (C₃-C₆)alkyl, hydroxy, methoxy, ethoxy, linearor branched (C₃-C₆)alkyloxy, (C₂-C₆)acyl, (C₂-C₆)acyloxy, phenyl andphenoxy; or one of R₁ or R₂ taken together with one of R₃ or R₄ and thecarbon atoms to which they are attached to form a (C₅-C₇)carbocyclicring optionally containing one or more double bonds; b) optionally oneor more monomers of formula (IV):

wherein R₁₆ and R₁₇ are the same or different and each independentlyselected from the group consisting of hydrogen, methyl ethyl, linear orbranched (C₃-C₆)alkyl, methoxy, ethoxy, linear or branched(C₃-C₆)alkyloxy, acetoxy, (C₂-C₆)acyl, phenyl and phenoxy; or R₁₆ takentogether with R₁₇ and the carbon atoms to which they are attached toform a (C₅-C₇)carbocyclic ring optionally containing one or more doublebonds; R₁₈ is hydrogen, halogen, methyl, ethyl, linear or branched(C₃-C₁₆)alkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₆)alkyl, hydroxy, methoxy,ethoxy, linear or branched (C₃-C₁₆)alkoxy, (C₆-C₁₀)aryloxy,(C₆-C₁₀)aryl(C₁-C₆)alkoxy, —O(CO)R₁₉ and —O(CO)OR₁₉, where R₁₉ ismethyl, ethyl, linear or branched (C₃-C₁₆)alkyl, (C₆-C₁₀)aryl and(C₆-C₁₀)aryl(C₁-C₆)alkyl; and c) a compound of formula (V):

wherein X is hydrogen or chlorine; R₃₀ and R₃₁ are the same or differentand independently of each other selected from the group consisting ofhydrogen, chlorine, methyl, ethyl, linear or branched (C₃-C₁₂)alkyl,(C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl,(C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₁-C₁₂)alkoxy,(C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy,(C₆-C₁₀)aryloxy(C₁-C₃)alkyl and (C₆-C₁₀)-aryloxy; wherein said latentorgano-ruthenium carbide catalyst is of formula (II):

wherein: L is PR₃, where R is independently selected from the groupconsisting of isopropyl, sec-butyl, tert-butyl, cyclohexyl,bicyclo(C₅-C₁₀)alkyl, phenyl, benzyl, isopropoxy, sec-butoxy,tert-butoxy, cyclohexyloxy, phenoxy and benzyloxy; R₇ is selected fromthe group consisting of methyl, ethyl, isopropyl, sec-butyl, tert-butyl,substituted or unsubstituted cyclohexyl, substituted or unsubstitutedphenyl, substituted or unsubstituted biphenyl and substituted orunsubstituted naphthyl; Ar₁ is selected from the group consisting ofsubstituted or unsubstituted phenyl, substituted or unsubstitutedbiphenyl and substituted or unsubstituted naphthyl; wherein substituentsare selected from the group consisting of methyl, ethyl, iso-propyl,tert-butyl and phenyl; and wherein said component A and said component Bare in a clear liquid form having a viscosity below 100 centipoise at25° C.
 17. The kit according to claim 16, which contains a compound offormula (V) selected from the group consisting of:


18. The kit according to claim 16, wherein the photoactive acidgenerator is selected from the group consisting of:

where R₃₅ and R₃₆ are the same or different and each independentlyselected from linear or branched (C₁₀-C₁₃)alkyl; and


19. The kit according to claim 16, which contains a mixture selectedfrom the group consisting of: component A containing a mixture of5-phenethylbicyclo[2.2.1]hept-2-ene,1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-tricyclohexylphosphine-rutheniumcarbide dichloride and 1-chloro-4-propoxy-9H-thioxanthen-9-one, andcomponent B containing tolylcumyliodonium-tetrakispentafluorophenylborate and toluene; component A containing a mixture of5-phenethylbicyclo[2.2.1]hept-2-ene,1,3-bis(2,6-diisopropylphenylimidazolidin-2-ylidene)-tricyclohexylphosphine-rutheniumcarbide dichloride and 1-chloro-4-propoxy-9H-thioxanthen-9-one, andcomponent B containing a mixture of tolylcumyliodonium-tetrakispentafluorophenylborate and toluene; component A containing a mixture of5-phenethylbicyclo[2.2.1]hept-2-ene,1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-tricyclohexylphosphine-rutheniumcarbide dichloride and 1-chloro-4-propoxy-9H-thioxanthen-9-one, andcomponent B containing a mixture of5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene andtolylcumyliodonium-tetrakis pentafluorophenylborate; and component Acontaining a mixture of 5-phenethylbicyclo[2.2.1]hept-2-ene,dicyclopentadiene,1,3-bis(2,6-diisopropylphenylimidazolidin-2-ylidene)-tricyclohexylphosphine-rutheniumcarbide dichloride and 1-chloro-4-propoxy-9H-thioxanthen-9-one; andcomponent B containing a mixture of tolylcumyliodonium-tetrakispentafluorophenylborate and5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene.
 20. Athree dimensional object comprising the composition of claim 1.